Disclosed is a process of preparing a planographic printing plate from a light sensitive planographic printing plate material comprising a hydrophilic support and provided thereon, an image formation layer containing (A) a polymerization initiator selected from an arene-iron complex and a tribromoacetyl compound, (B) a polymerizable ethylenically unsaturated compound, and (C) an alkali soluble resin with an acid value of 5 to 200, the process comprising the steps of imagewise exposing the light sensitive planographic printing plate material to ultraviolet light using an exposure device comprising a digital mirror device (DMD), and removing an image formation layer at non-exposed portions with an aqueous alkali solution to form an image.
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1. A process of preparing a planographic printing plate from a light sensitive planographic printing plate material comprising a hydrophilic support and provided thereon, an image formation layer containing (A) a tribromoacetyl compound, (B) a polymerizable ethylenically unsaturated compound, and (C) an alkali soluble resin, the process comprising the steps of:
imagewise exposing the light sensitive planographic printing plate material to ultraviolet light using an exposure device comprising a digital mirror device (DMD); and
removing an image formation layer at non-exposed portions with an aqueous alkali solution to form an image.
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The present invention relates to a process of preparing a planographic printing plate.
Hitherto, an image formation method has been carried out in a conventional photographic plate making, which comprises bringing a light sensitive planographic printing plate material into contact with an original with an image, and exposing to light through the original. Recently, a computer to plate (hereinafter referred as to CTP) system has spread which comprises recording directly a digital image onto a light sensitive planographic printing plate material employing a laser. However, in order to carry out scanning exposure in a short time employing a laser, not only a laser with high output power but a light sensitive planographic printing plate material for CTP having sensitivity of 1,000 to 10,000 times the sensitivity of a conventional contact exposure type light sensitive planographic printing plate material are required. A planographic printing plate material for CTP with such a high sensitivity is expensive, and has problem in that sensitivity varies after long term storage.
A method is proposed in which digital signals are recorded on a light sensitive planographic printing plate material employing an ultraviolet lamp as a light source. This method is advantageous in view of cost reduction, since it is possible to use a conventional contact exposure type light sensitive planographic printing plate material having sensitivity in ultraviolet regions. However, this method has problem that exposure time takes several times that in a conventional contact exposure. Thus, a light sensitive planographic printing plate material is required which has high sensitivity in the ultraviolet regions.
In Japanese Patent O.P.I. Publication No. 2004-29296 is disclosed a method of preparing a printing plate from a planographic printing plate material comprising a hydrophilic support and an image formation layer containing a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and a sensitizing dye having a specific structure, the method comprising the step of exposing the planographic printing plate material to ultraviolet rays corresponding to image data employing a DMD to polymerize the polymerizable ethylenically unsaturated compound. A printing plate prepared according to this method provides high printing durability, but has problem in printing durability. In Japanese Patent O.P.I. Publication No. 2004-20623 is disclosed a method of preparing a printing plate from a planographic printing plate material comprising a curable resin, the method comprising the step of exposing the planographic printing plate material to ultraviolet rays corresponding to image data employing a DMD, while heating, wherein curable resin at exposed portions are cured. This method provides a printing plate high printing durability, but has problem in that a heating system for heating the planographic printing plate material is complicate and impracticable, and the heating temperature is difficult to control, resulting in instability of image forming conditions. Further, a printing plate prepared according to this method has poor chemical resistance, and has problem in that when in a printing process ink stains at the non-image portions are removed employing a cleaning solution, so-called a plate cleaner, image portions, particularly small dots are likely to disappear.
In view of the above, the present invention has been made. An object of the invention is to provide a process of preparing, in a short time, a planographic printing plate with high chemical resistance and high printing durability from a planographic printing plate material, employing a digital mirror device (DMD) in a CTP system.
The above object has been attained by one of the following constitutions:
1-1. A process of preparing a planographic printing plate from a light sensitive planographic printing plate material comprising a hydrophilic support and provided thereon, an image formation layer containing (A) at least one polymerization initiator selected from an arene-iron complex and a tribromoacetyl compound, (B) a polymerizable ethylenically unsaturated compound, and (C) an alkali soluble resin with an acid value of 5 to 200, the process comprising the steps of imagewise exposing the light sensitive planographic printing plate material to ultraviolet light using an exposure device comprising a digital mirror device (DMD), and removing an image formation layer at non-exposed portions with an aqueous-alkali solution to form an image.
1-2. The process of item 1-1 above, wherein the weight average molecular weight of the alkali soluble resin is in the range of from 5,000 to 200,000.
1-3. The process of item 1-1 above, wherein the alkali soluble resin has both carbonyl group and a polymerizable double bond in the molecule.
1-4. The process of item 1-1 above, wherein the image formation layer contains the polymerization initiator in an amount of from 1 to 20% by weight, the polymerizable ethylenically-unsaturated compound in an amount of from 10 to 70% by weight, and the alkali soluble resin in an amount of from 10 to 90% by weight.
1-5. The process of item 1-1 above, wherein the image formation layer further contains a sensitizing dye.
1-6. The process of item 1-5 above, wherein the sensitizing dye has an absorption maximum in the range of from 350 to 450 nm.
1-7. The process of item 1-1 above, wherein a protective layer containing polyvinyl alcohol and polyvinyl pyrrolidone is provided on the image formation layer.
1-8. The process of item 1-1 above, wherein the DMD is comprised of a lot of micro-mirrors, which reflect ultraviolet light.
1-9. The process of item 1-1 above, wherein the exposure device further comprises a light source element and an image formation element.
1-10. The process of item 1-1 above, wherein the ultraviolet light is light having a wavelength of 350 to 450 nm.
Next, the present invention will be explained in detail.
In view of the above, the present inventor has made an extensive study. As a result, the present inventor has found a process of preparing, from a light sensitive planographic printing plate material, a planographic printing plate with high chemical resistance and high printing durability in a short time, employing an exposure device comprising a digital mirror device (DMD) in a CTP system, and completed the invention. The process comprises the steps of imagewise exposing the light sensitive planographic printing plate material employing an exposure device comprising a DMD, and removing an image formation layer at non-exposed portions with an aqueous alkali solution to form an image, the light sensitive planographic printing plate material comprising a hydrophilic support and provided thereon, an image formation layer containing (A) at least one polymerization initiator selected from an arene-iron complex a-1 and a tribromoacetyl compound a-2, (B) a polymerizable ethylenically unsaturated compound and (C) an alkali soluble resin with an acid value of 5 to 200.
The present invention will be detailed below.
The light sensitive planographic printing plate material in the invention comprises an image formation layer containing (A) at least one polymerization initiator selected from an arene-iron complex a-1 and a tribromoacetyl compound a-2, (B) a polymerizable ethylenically unsaturated compound and (C) an alkali soluble resin.
[Polymerization Initiator]
The polymerization initiator in the invention will be detailed below.
The image formation layer in the invention contains at least one polymerization initiator selected from an iron-arene complex and a tribromoacetyl compound.
Iron-arene Complex a-1
As the iron-arene complex used in the invention, there are those disclosed in Japanese Patent O.P.I. Publication Nos. 59-219307. Preferred examples of the iron-arene complex include η-benzene-(η-cyclopentadienyl)iron hexafluorophosphate, η-cumene-(η-cyclopentadienyl)iron hexafluorophosphate, η-fluorene-(η-cyclopentadienyl)iron hexafluorophosphate, η-naphthalene-(η-cyclopentadienyl)iron hexafluorophosphate, η-xylene-(η-cyclopentadienyl)iron hexafluorophosphate, and η-benzene-(η-cyclopentadienyl)iron tetrafluoroborate.
Tribromoacetyl Compound a-2
As the tribromoacetyl compound used in the invention, there are for example, tribromoacetoaldehyde, tribromoacetic acid, tribromoacetophenone, tribromoacetylthiophene, a tribromoacetate compound obtained by reacting alcohols with tribromoacetyl chloride, and a tribromoacetamide compound obtained by reacting amines with tribromoacetyl chloride.
Examples of the tribromoacetyl compound will be listed below, but the invention is not limited thereto.
##STR00001## ##STR00002## ##STR00003## ##STR00004## ##STR00005## ##STR00006## ##STR00007##
The content of the iron-arene complex a-1 or tribromoacetyl compound a-2 in the image formation layer is preferably from 1 to 20% by weight. When these two polymerization initiators are used, each is contained in an amount of preferably from 1 to 20%. by weight in the image formation layer.
(Other Polymerization Initiators)
The image formation layer in the invention can contain other photopolymerization initiators together with the hexaarylbisimidazole compound or diazo resin in the invention.
Examples of the other photopolymerization initiators include radical generating compounds disclosed in Japanese Patent Publication No. 2002-537419, polymerization initiators disclosed in Japanese Patent O.P.I. Publication Nos. 2001-175006, 2002-278057, and 2003-5363, onium salts having two or more cation portions in the molecule disclosed in Japanese Patent O.P.I. Publication No. 2003-76010, N-nitroso amine compounds disclosed in Japanese Patent O.P.I. Publication No. 2001-133966, thermally radical generating compounds disclosed in Japanese Patent O.P.I. Publication No. 2001-343742, compounds of generating a radical or an acid by heat disclosed in Japanese Patent O.P.I. Publication No. 2002-6482, borate compounds disclosed in Japanese Patent O.P.I. Publication No. 2002-116539, compounds of generating a radical or an acid by heat disclosed in Japanese Patent O.P.I. Publication No. 2002-148790, photopolymerization initiators or thermal polymerization initiators each having a polymerizable unsaturated group disclosed in Japanese Patent O.P.I. Publication No. 2002-207293, onium salts having, as a counter ion, a divalent or more valent anion disclosed in Japanese Patent O.P.I. Publication No. 2002-268217, sulfonylsulfone compounds having a specific structure disclosed in Japanese Patent O.P.I. Publication No. 2002-328465, thermally radical generating compounds disclosed in Japanese Patent O.P.I. Publication No. 2002-341519, and hexaarylbisimidazole compounds disclosed in Japanese Patent O.P.I. Publication Nos. 2002-295426.
Preferred examples of the other photopolymerization initiators include a triarylsulfonium salt, a diaryliodonium salt, a titanocene compound, a trihalomethyltriazine compound, an acylphosphine oxide compound, a benzoin derivative, or at N-phenylglycine derivative, and are not limited thereto.
Diazo resins, for example, those disclosed in Japanese Patent O.P.I. Publication No. 10-313017, can be preferably used as the other polymerization initiator.
The content of the other photopolymerization initiator in the image formation layer, which can be used in combination with polymerization initiators (a-1) or (a-2), is not specifically limited, but is preferably from 0.1 to 20% by weight, and more preferably from 0.8 to 15% by weight.
[Sensitizing Dye]
The image formation layer in the invention can contain a sensitizing dye in order to accelerate polymerization. Since ultraviolet rays are used as light for recording an image, a sensitizing dye absorbing the ultraviolet rays is preferred. Typically, a sensitizing dye is preferred which has an absorption maximum at wavelength regions of from 350 to 450 nm; and more preferably from 350 to 410 nm.
Examples thereof include optical whitening dyes disclosed in Japanese Patent O.P.I. Publication No. 2003-295426, sensitizing dyes disclosed in Japanese Patent O.P.I. Publication No. 2003-21901, compounds represented by formula (I) disclosed in Japanese Patent O.P.I. Publication No. 2003-21895, compounds represented by formula (I) disclosed in Japanese Patent O.P.I. Publication No. 2003-21894, sensitizing dyes having a specific chemical structure disclosed in Japanese Patent O.P.I. Publication No. 2003-351702, sensitizing dyes-having a specific chemical structure disclosed in Japanese Patent O.P.I. Publication No. 2003-351701, sensitizing dyes having a specific chemical structure (a pyrrolopyrrole ring) disclosed in Japanese Patent O.P.I. Publication No. 2003-351065, sensitizing dyes disclosed in Japanese Patent O.P.I. Publication Nos. 2002-268239, and 2002-268204, compounds represented-by formula (I) disclosed in Japanese Patent O.P.I. Publication No. 2002-221790, compounds represented by formula (I) disclosed in Japanese Patent O.P.I. Publication No. 2002-202598, carbazole type sensitizing dyes disclosed in Japanese Patent O.P.I. Publication No. 2001-042524, sensitizing dyes disclosed in Japanese Patent O.P.I. Publication Nos. 2000-309724 and 2000-258910, naphtho[1,8-bc]furan-5-on derivatives disclosed in Japanese Patent O.P.I. Publication Nos. 2000-206690, merocyanine dyes disclosed in Japanese Patent O.P.I. Publication Nos. 2000-147763, and carbonyl compounds disclosed in Japanese Patent O.P.I. Publication Nos. 2000-098605.
Preferred examples of the sensitizing dye include coumarin compounds represented by formulas Dye 01 through 08 below, merocyanine dyes represented by formulas Dye 09 through 11 below, boron-contained compounds represented by formulas Dye 12 through 14 below, styryl dyes represented by formulas Dye 15 and 16 below, pyrylium salts represented by formulas Dye 17 and 18 below, and cyanine dyes represented by formulas Dye 19 through 24 below. Dyes 01 through 24 are listed below. The present invention is not limited thereto.
##STR00008## ##STR00009## ##STR00010##
The content of the sensitizing dye in image formation layer is not specifically limited, but is preferably from 0.1 to 20% by weight, and more preferably from 0.8 to 15% by weight. The content of the sensitizing dye is a content providing an absorbance of preferably from 0.2 to 2.0, and more preferably from 0.3 to 1.2 in the reflection spectrum measured employing an integrating sphere. These sensitizing dyes can be used singly or in combination.
[Polymerizable Ethylenically Unsaturated Compound]
In the invention, the image formation layer can contain a polymerizable ethylenically unsaturated compound, so-called a monomer or a polyfunctional oligomer. The content of the monomer or polyfunctional oligomer in the image formation layer is preferably from 10 to 70% by weight, and more preferably from 20 to 60% by weight.
As the monomer or polyfunctional oligomer, there are a conventional radical polymerizable monomer, and a polyfunctional monomer or oligomer having two or more of an ethylenic double bond in the molecule as generally used in an ultraviolet curable resin composition.
The monomer or polyfunctional oligomer is not specifically limited. Preferred examples thereof include a monofunctional acrylate such as 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryl-oxyethyl acrylate, tetrahydrofurfuryloxyhexanorideacrylate, an ester of 1,3-dioxane-ε-caprolactone adduct with acrylic acid, or 1,3-dioxolane acrylate; a methacrylate, itaconate, crotonate or maleate alternative of the above acrylate; a bifunctional acrylate such as ethyleneglycol diacrylate, triethyleneglycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, neopentyl glycol adipate diacrylate, diacrylate of hydroxypivalic acid neopentyl glycol-ε-caprolactone adduct, 2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecanedimethylol acrylate, tricyclodecanedimethylol acrylate-ε-caprolactone adduct or 1,6-hexanediol diglycidylether diacrylate; a dimethacrylate, diitaconate, dicrotonate or dimaleate alternative of the above diacrylate; a polyfunctional acrylate such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexacrylate, dipentaerythritol hexacrylate-ε-caprolactone adduct, pyrrogallol triacrylate, propionic acid dipentaerythritol triacrylate, propionic acid dipentaerythritol tetraacrylate or hydroxypivalylaldehyde modified dimethylolpropane triacrylate; a methacrylate, itaconate, crotonate or maleate alternative of the above polyfunctional acrylate.
Prepolymers can be used, and examples thereof include prepolymers described later. These prepolymers can be used singly, in combination, or as an admixture thereof with the above described monomer and/or oligomer.
Examples of the prepolymer include polyester (meth)acrylate obtained by incorporating (meth)acrylic acid in a polyester of a polybasic acid such as adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumalic acid, pimelic acid, sebatic acid, dodecanic acid or tetrahydrophthalic acid with a polyol such as ethylene glycol, ethylene glycol, diethylene glycol, propylene oxide, 1,4-butane diol, triethylene glycol, tetraethylene glycol, polyethylene glycol, grycerin, trimethylol propane, pentaerythritol, sorbitol, 1,6-hexanediol or 1,2,6-hexanetriol; an epoxyacrylate such as bisphenol A.epichlorhydrin.(meth)acrylic acid or phenol novolak.epichlorhydrin.(meth)acrylic acid obtained by incorporating (meth)acrylic acid in an epoxy resin; an urethaneacrylate such as ethylene glycol.adipic acid tolyleneduisocyanate.2-hydroxyethylacrylate, polyethylene glycol.tolylenediisocyanate-2-hydroxyethylacrylate, hydroxyethylphthalyl methacrylate.xylenediisocyanate, 1,2-polybutadieneglycol. tolylenediisocyanate.2-hydroxyethylacrylate or trimethylolpropane.propylene glycol.tolylenediisocyanate.2-hydroxyethylacrylate, obtained by incorporating (meth)acrylic acid-in an-urethane resin; a silicone acrylate such as polysiloxane acrylate, or polysiloxane.diisocyanate.2-hydroxyethylacrylate; an alkyd modified acrylate obtained by incorporating a methacroyl group in an oil modified alkyd resin; and a spirane resin acrylate.
The image formation layer in the invention may contain a monomer such as a phosphazene monomer, triethylene glycol di(meth)acrylate, an EO modified isocyanuric acid diacrylate, an EO modified isocyanuric acid triacrylate, dimethyloltricyclodecane diacrylate, trimethylolpropane acrylate benzoate, an alkylene glycol acrylate, or a urethane modified acrylate, or an addition polymerizable oligomer or prepolymer having a structural unit derived from the above monomer.
The ethylenic monomer used in the invention is a phosphate compound having at least one (meth)acryloyl group. The phosphate compound is a compound having a (meth)acryloyl group in which at least one hydroxyl group of phosphoric acid is esterified.
Besides the above compounds, compounds disclosed in Japanese Patent O.P.I. Publication Nos. 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63-67189, and 1-244891, compounds described on pages 286 to 294 of “11290 Chemical Compounds” edited by Kagakukogyo Nipposha, and compounds described on pages 11 to 65 of “UV.EB Koka Handbook (Materials)” edited by Kobunshi Kankokai can be suitably used. Of these compounds, compounds having two or more acryl or methacryl groups in the molecule are preferable, and those having a molecular weight of not more than 10,000, and preferably not more than 5,000 are more preferable.
In the invention, an addition polymerizable ethylenically unsaturated monomer having a tertiary amino group in the molecule is preferably used as the polymerizable ethylenically unsaturated compound. Its molecular structure is not limited, but those are preferred in which a tertiary amine having a hydroxyl group is modified with glycidyl methacrylate, methacrylic chloride, or acrylic chloride. Examples thereof include a polymerizable compound disclosed in Japanese Patent O.P.I. Publication Nos. 1-165613, and Japanese Patent Publication Nos. 1-203413 and 1-197213.
A reaction product of (i) a polyhydric alcohol having a tertiary amino group in the molecule, (ii) a diisocyanate, and (iii) a compound having both hydroxyl group and addition polymerizable ethylenically double bond in the molecule is preferably used in the invention. Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-tert-butyldiethanolamine, N,N-di(hydroxyethyl)aniline, N,N, N′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N,N, N′,N′-tetra-2-hydroxyethylethylenediamine, N,N-bis(2-hydroxypropyl)aniline, allyldiethanolamine, 3-dimethylamino-1,2-propane diol, 3-diethylamino-1,2-propane diol, N,N-di(n-propylamino)-2,3-propane diol, N,N-di(iso-propylamino)-2,3-propane diol, and 3-(N-methyl-N-benzylamino)-1,2-propane diol.
Examples of the diisocyanate include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanatomethylcyclohexanone, 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di(isocyanatomethyl)benzene, and 1,3-bis(1-isocyanato-1-methylethyl)benzene, but the invention is not specifically limited thereto. Examples of the compound having a hydroxyl group and an addition polymerizable ethylenically double bond in the molecule include compounds MH-1 through MH-13 as described later.
The chemical structure of MH-1 through MH-13 will be shown below.
##STR00011## ##STR00012##
Preferred examples thereof include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, and 2-hydroxypropylene-1-methacrylate-3-acrylate.
The reaction product above can be synthesized according to the same method as a conventional method in which a urethaneacrylate compound is ordinarily synthesized employing an ordinary diol, a diisocyanate and an actylate having a hydroxyl group.
Examples of the reaction product of a polyhydric alcohol having a tertiary amino group in the molecule, a diisocyanate and a compound having a hydroxyl group and an addition polymerizable ethylenically double bond in the molecule will be listed below.
In addition to the above, acrylates or methacrylates disclosed in Japanese Patent O.P.I. Publication Nos. 1-105238 and 2-127404 can be used.
[Alkali Soluble Resin as Binder]
The image formation layer in the invention contains an alkali soluble resin as a binder. The weight average molecular weight of the alkali soluble resin in the invention is not specifically limited, but is in the range of from preferably 5,000 to 200,000, and more preferably from preferably 10,000 to 100,000. The alkali soluble resin in the invention has an acid value of preferably from 5 to 200, more preferably from 10 to 150, and most preferably 10 to 120.
As the alkali soluble resin in the invention can be used a polyacrylate resin, a polyurethane resin, a polyamide resin, a polyester resin, an epoxy resin, a phenol resin, a polycarbonate resin, a polyvinyl butyral resin, a polyvinyl formal resin, a shellac resin, or another natural resin. These resins can be used singly or as an admixture of two or more thereof.
The alkali soluble resin in the invention is preferably a copolymer obtained by copolymerization of an acryl or methacryl monomer with another monomer, and more preferably a copolymer containing (a) a carboxyl group-containing monomer unit and (b) an alkyl methacrylate or alkyl acrylate unit as the copolymerization component.
Examples of the carboxyl group-containing monomer include an α, β-unsaturated carboxylic acid, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride or a carboxylic acid such as a half ester of phthalic acid with 2-hydroxyethyl methacrylate.
Examples of the alkyl methacrylate or alkyl acrylate include an unsubstituted alkyl ester such as methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, amylmethacrylate, hexylmethacrylate, heptylmethacrylate, octylmethacrylate, nonylmethacrylate, decylmethacrylate, undecylmethacrylate, dodecylmethacrylate, methylacrylate, ethylacrylate, propylacrylate, butylacrylate, amylacrylate, hexylacrylate, heptylacrylate, octylacrylate, nonylacrylate, decylacrylate, undecylacrylate, or dodecylacrylate; a cyclic alkyl ester such as cyclohexyl methacrylate or cyclohexyl acrylate; and a substituted alkyl ester such as benzyl methacrylate, 2-chloroethyl methacrylate, N,N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate or N,N-dimethylaminoethyl acrylate.
The copolymer described above can further contain another comonomer unit.
Examples of such a comonomer include monomers described in the following items (1) through (14).
1) A monomer having an aromatic hydroxy group, for example, o-, (p- or m-) hydroxystyrene, or o-, (p- or m-) hydroxyphenylacrylate;
2) A monomer having an aliphatic hydroxy group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, or hydroxyethyl vinyl ether;
3) A monomer having an aminosulfonyl group, for example, m- or p-aminosulfonylphenyl methacrylate, m- or p-aminosulfonylphenyl acrylate, N-(p-aminosulfonylphenyl) methacrylamide, or N-(p-aminosulfonylphenyl)acrylamide;
4) A monomer having a sulfonamido group, for example, N-(p-toluenesulfonyl)acrylamide, or N-(p-toluenesulfonyl)-methacrylamide;
5) An acrylamide or methacrylamide, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N-4-hydroxyphenylacrylamide, or N-4-hydroxyphenylmethacrylamide;
6) A monomer having a fluorinated alkyl group, for example, trifluoromethyl acrylate, trifluoromethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, heptadecafluorodecyl methacrylate, or N-butyl-N-(2-acryloxyethyl)heptadecafluorooctylsulfonamide;
7) A vinyl ether, for example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, or phenyl vinyl ether;
8) A vinyl ester, for example, vinyl acetate, vinyl chroloacetate, vinyl butyrate, or vinyl benzoate;
9) A styrene, for example, styrene, methylstyrene, or chloromethystyrene;
10) A vinyl ketone, for example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or phenyl vinyl ketone;
11) An olefin, for example, ethylene, propylene, isobutylene, butadiene, or isoprene;
12) N-vinylpyrrolidone, N-vinylcarbazole, or N-vinylpyridine,
13) A monomer having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butene nitrile, 2-cyanoethyl acrylate, or o-, m- or p-cyanostyrene;
14) A monomer having an amino group, for example, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N,N-dimethylaminopropyl acrylamide, N,N-dimethylacrylamide, acryloylmorpholine, N-isopropylacrylamide, or N,N-diethylacrylamide.
The copolymer above can be prepared by a conventional solution polymerization, a bulk polymerization or an emulsion polymerization. The polymerization initiators used are not specifically limited, and include 2,2′-azobisisobutyronitrile (AIBN), and 2,2′-azobis(2-methylbutyronitrile). The polymerization initiator is used in an amount of from 0.05 to 10.0 parts by weight, and preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the total monomer used in polymerization. As the solvents used in the solution polymerization, there are organic solvents of ketone type, ester type or aromatic hydrocarbon type. Examples thereof include toluene, ethyl acetate, benzene, methylcellosolve, ethylcellosolve, acetone, and methyl ethyl ketone, which are good solvents for (meth)acryl polymers. Among these, solvents with a boiling point of from 60 to 120° C. are preferred. Solution polymerization is carried out at a temperature of from 40 to 120° C., and preferably from 60 to 110° C. for 3 to 10 hours, preferably 5 to 8 hours. After the polymerization is completed in the solution polymerization to obtain a polymer solution, the solvents in the polymer solution are removed to obtain a polymer. The polymer solution can be used without removing the solvents for the subsequent incorporation reaction of a double bond described later.
The molecular weight of the polymer can be controlled by kinds of solvents used or polymerization temperature. The polymerization solvents used or polymerization temperature for preparing a polymer having an intended molecular weight can be suitably determined due to kinds of monomers used. The molecular weight of the polymer can be controlled by addition of a specific organic solvent to the polymerization solvents. Examples of the specific solvent include mercaptans such as n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and mercaptoethanol; and chlorine-containing solvents such as carbon tetrachloride, butyl chloride, and propylene chloride. A mixing ratio of the specific solvent to the polymerization solvent can be suitably determined due to kinds of monomers or polymerization solvents used or polymerization conditions.
The alkali soluble resin in the invention is preferably a copolymer having a carboxyl group and a polymerizable double bond in the side chain. The copolymer is preferably a double bond-containing copolymer which is obtained by reacting a polymer having a carboxyl group with a compound having a polymerizable double bond and an epoxy group in the molecule. Examples of the compound having a polymerizable double bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and epoxy group-containing unsaturated compounds disclosed in Japanese Patent O.P.I. Publication No. 11-271969. The copolymer is preferably a double bond-containing copolymer which is obtained by reacting a polymer having a hydroxyl group with a compound having a (meth)acryloyl group and an isocyanate group in the molecule. Examples of the compound having a (meth)acryloyl group and an isocyanate group in the molecule include vinyl isocyanate, (meth)acryl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and m- or p-isopropenyl-α,α′-dimetylbenzyl isocyanate.
A method is well known which reacts a polymer having a carboxyl group with a compound having a (meth)acryloyl group and an epoxy group in the molecule. The reaction is carried out at from 20 to 100° C., preferably from 40 to 80° C. and more preferably a boiling point of solvents used for 2 to 10 hours, preferably 3 to 6 hours. Solvents used include the same as those used in the polymerization described above. A polymer solution obtained after solution polymerization, in which the polymer is dissolved in a solvent, can be used without removing the solvent for reacting the polymer with the epoxy group-containing compound. The reaction is carried out optionally in the presence of a catalyst or a polymerization inhibitor. As the catalysts, there are amine compounds or ammonium chloride compounds. Examples of the amine compound include triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine, isopropylamine, 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, and benzylamine. Examples of the ammonium chloride compounds include triethylbenzylammonium chloride. The catalyst is used in an amount of from 0.01 to 20.0% by weight, based on the weight of the compound having a polymerizable double bond and an epoxy group in the molecule (an epoxy group-containing unsaturated compound). Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyltoluene. The polymerization inhibitor is used in an amount of from 0.01to 5.0% by weight, based on the weight of the compound having a polymerizable double bond and an epoxy group in the molecule.
A method is well known which reacts a polymer having a hydroxyl group with a compound having a (meth)acryloyl group and an isocyanate group in the molecule. The reaction is carried out at from 20 to 100° C., preferably from 40 to 80° C. and more preferably a boiling point of solvents used for 2 to 10 hours, preferably 3 to 6 hours. Solvents used include the same as those used in the polymerization described above. A polymer solution obtained after solution polymerization, in which the polymer is dissolved in a solvent, can be used without removing the solvent for reacting the polymer with the isocyanate group-containing unsaturated compound. The reaction is carried out optionally in the presence of a catalyst or a polymerization inhibitor. The catalyst is preferably a tin-contained compound or amines, and examples thereof include dibutyltin laurate and triethylamine. The catalyst is used in an amount of preferably from 0.01 to 20.0% by weight of the compound having a (meth)acryloyl group and an isocyanate group in the molecule (a compound having a double bond). Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyltoluene. The polymerization inhibitor is used in an amount of from 0.01 to 5.0% by weight, based on the weight of the compound having a polymerizable double bond and an isocyanate group in the molecule.
The reaction process is controlled while measuring IR spectra of the reaction mixture to observe absorption of the isocyanate group, and the reaction is stopped at the time when absorption of the isocyanate group is not observed.
The content in the image formation layer of the copolymer having a carboxyl group and a polymerizable double bond in the side chain is preferably from 50 to 100% by weight, and more preferably 100% by weight, based on the weight of the total alkali soluble resin contained in the image formation layer.
The content of the alkali soluble resin in the image formation layer is preferably from 10 to 90% by weight, more preferably from 10 to 70% by weight, and most preferably from 20 to 50% by weight in view of sensitivity.
[Amino Compound]
The image formation layer in the invention can contain an amino compound.
The amino compound used in the invention is not specifically restricted. As the amino compound, a compound represented by formula (I) below and its multimers are preferred.
##STR00013##
In formula (I), n represents an integer of from 1 to 10; R1 through R5 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxyl group, a cyano group, a nitro group, a sulfo group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted acryloyloxy group, a substituted or unsubstituted alkylcarbonyloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted amino group or a substituted or unsubstituted amido group.
R6 and R7 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted aryloxy group.
It is preferred that R1 through R5 independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having a carbon atom number of from 1 to 10 and preferably from 1 to 5, or a substituted or unsubstituted alkoxy group having a carbon atom number of from 1 to 10 and preferably from 1 to 5.
It is preferred that R6 and R7 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having a carbon atom number of from 1 to 10, a substituted or unsubstituted alkenyl group having a carbon atom number of from 2 to 10, a substituted or unsubstituted aryl group having a carbon atom number of from 6 to 10, or a substituted or unsubstituted acryloyl. It is more preferred that R6 and R7 independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having a carbon atom number of from 1 to 10, and preferably from 1 to 5.
Examples of the substituent of the substituted groups above include an alkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an alkylcarbonyloxy group, an acryloyloxy group, a halogen atom, an amino group, an amido group, an acryloyl group, an acryloyloxy group, or a hydroxyl group. These substituents may further have a substituent. Among these substituents described above, an alkyl group, an aryl group, an amino group, an amido group, an alkoxycarbonyl group or a hydroxyl group is preferred.
The multimers of the compound represented by formula (I) above is a compound in which tow or more of the compound represented by formula (I) are combined directly or through a linkage group at the position of at least one of R1 through R7 thereof. The linkage group is not limited, as long as it is a polyvalent. The multimers are preferably a dimer, a trimer, a tetramer, or a pentamer.
Examples of the compound represented by formula (I) and its multimers will be listed below, but are not limited thereto.
##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
The compound represented by formula (I) or its multimers may be used singly or as a mixture of two or more kinds thereof.
The content of the amino compound in the image formation layer is preferably from 0.1 to 10% by weight, and more preferably from 0.5 to 5% by weight.
[Mercaptan]
The image formation layer in the invention can contain a mercaptan. Examples of the mercaptan include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzodiazole. The content of the mercaptan in the invention is preferably from 0.2 to 10% by weight, and more preferably from 0.5 to 5% by weight.
(Other Additives in the Image Formation Layer)
The image formation layer in the invention is preferably added with a polymerization inhibitor, in order to prevent undesired polymerization of the ethylenically unsaturated monomer during the manufacture or after storage of light sensitive planographic printing plate material. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerous salt, and 2-t-butyl-6-(3-t-butyl-6-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate.
The polymerization inhibitor content is preferably 0.01 to 5% by weight based on the total solid content of the light sensitive layer. Further, in order to prevent undesired polymerization induced by oxygen, behenic acid or a higher fatty acid derivative such as behenic amide may be added to the layer. After the light sensitive layer is coated layer, the coated layer may be dried so that the higher fatty acid derivative is localized at the vicinity of the surface of the light sensitive layer. The content of the higher fatty acid derivative is preferably 0.5 to 10% by weight, based on the total solid content of the light sensitive layer.
A colorant can be also used. As the colorant can be used known materials including commercially available materials. Examples of the colorant include those described in revised edition “Ganryo Binran”, edited by Nippon Ganryo Gijutu Kyoukai (published by Seibunndou Sinkosha), or “Color Index Binran”. Pigment is preferred.
Kinds of the pigment include black pigment, yellow pigment, red pigment, brown pigment, violet pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Examples of the pigment include inorganic pigment (such as titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, or chromate of lead, zinc, barium or calcium); and organic pigment (such as azo pigment, thioindigo pigment, anthraquinone pigment, anthanthrone pigment, triphenedioxazine pigment, vat dye pigment, phthalocyanine pigment or its derivative, or quinacridone pigment). Among these pigment, pigment is preferably used which does not substantially have absorption in the absorption wavelength regions of a spectral sensitizing dye used according to a laser for exposure. The absorption of the pigment used is not more than 0.05, obtained from the reflection spectrum of the pigment measured employing an integrating sphere and employing light with the wavelength of the laser used. The pigment content is preferably 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight, based on the total solid content of the photopolymerizable light sensitive layer composition.
A surfactant may be added to the image formation layer in order to improve coatability of the layer. A preferred surfactant is a fluorine-contained surfactant.
Further, in order to improve physical properties of the cured light sensitive layer, the layer can contain an inorganic filler or a plasticizer such as dioctyl phthalate, dimethyl phthalate or tricresyl phosphate. The content of *such a material is preferably not more than 10% by weight, based on the total solid content of the light sensitive layer.
The solvents used in the preparation of the coating liquid for the image formation layer in the invention include an alcohol such as sec-butanol, isobutanol, n-hexanol, or benzyl alcohol; a polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, or 1,5-pentanediol; an ether such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, or tripropylene glycol monomethyl ether; a ketone or aldehyde such as diacetone alcohol, cyclohexanone, or methyl cyclohexanone; and an ester such as ethyl lactate, butyl lactate, diethyl oxalate, or methyl benzoate.
In the invention, a protective layer is preferably provided on the image formation layer. It is preferred that the protective layer (oxygen shielding layer) is highly soluble in the developer as described above (generally an alkaline solution). The protective layer preferably contains polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has the effect of preventing oxygen from transmitting and polyvinyl pyrrolidone has the effect of increasing adhesion between the oxygen shielding layer and the photopolymerizable light sensitive layer adjacent thereto.
Besides the above two polymers, the oxygen shielding layer may contain a water soluble polymer such as polysaccharide, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octacetate, ammonium alginate, sodium alginate, polyvinyl amine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, or a water soluble polyamide.
In the planographic printing plate material in the invention, adhesive strength between the protective layer and the image formation layer is preferably not less than 35 mN/mm, more preferably not less than 50 mN/mm, and still more preferably not less than 75 mN/mm. Preferred composition of the protective layer is disclosed in Japanese Patent O.P.I. Publication No. 10-10742. The adhesive strength in the invention can be measured according to the following procedure.
When an adhesive tape with sufficient adhesive strength having a predetermined width is adhered onto the protective layer, and then peeled at an angle of 90° to the plane of the planographic printing plate material, strength necessary to peel the protective layer from the image formation layer is measured as the adhesive strength.
The protective layer may further contain a surfactant or a matting agent. The protective layer is formed, coating on the photopolymerizable light sensitive layer a coating solution in which the above protective layer composition is dissolved in an appropriate coating solvent, and drying. The main solvent of the coating solution is preferably water or an alcohol solvent such as methanol, ethanol, or iso-propanol.
The thickness of the protective layer is preferably 0.1 to 5.0 μm, and more preferably 0.5 to 3.0 μm.
The supports in the invention include a plate having a hydrophilic surface of a metal such as aluminum, stainless steel, chromium, or nickel, a plastic film such as a polyester film, a polyethylene film or a polypropylene film which is deposited or laminated with the above-described metal, and a polyester film, a polyvinyl chloride film or a nylon film whose surface is subjected to hydrophilization treatment. Among the above, the aluminum plate is preferably used, and may be a pure aluminum plate or an aluminum alloy plate. As the aluminum alloy, there can be used various ones including an alloy of aluminum and a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium or iron.
It is preferable that the support in the invention is subjected to degreasing treatment for removing rolling oil prior to surface roughening (graining). The degreasing treatments include degreasing treatment employing solvents such as trichlene and thinner, and an emulsion degreasing treatment employing an emulsion such as kerosene or triethanol. It is also possible to use an aqueous alkali solution such as caustic soda for the degreasing treatment. When an aqueous alkali solution such as caustic soda is used for the degreasing treatment, it is possible to remove soils and an oxidized film which can not be removed by the above-mentioned degreasing treatment alone. When an aqueous alkali solution such as caustic soda is used for the degreasing treatment, the resulting support is preferably subjected to desmut treatment in an aqueous solution of an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixture thereof, since smut is produced on the surface of the support. The surface roughening methods include a mechanical surface roughening method and an electrolytic surface roughening method electrolytically etching the support surface.
Though there is no restriction for the mechanical surface roughening method, a brushing roughening method and a honing roughening method are preferable. The brushing roughening method is carried out by rubbing the surface of the support with a rotating brush with a brush hair with a diameter of 0.2 to 0.8 mm, while supplying slurry in which volcanic ash particles with a particle size of 10 to 100 μm are dispersed in water to the surface of the support. The honing roughening method is carried out by ejecting obliquely slurry with pressure applied from nozzles to the surface of the support, the slurry containing volcanic ash particles with a particle size of 10 to 100 μm dispersed in water. A surface roughening can be also carried out by laminating a support surface with a sheet on the surface of which abrading particles with a particle size of from 10 to 100 μm was coated at intervals of 100 to 200 μm and at a density of 2.5×103 to 10×103/cm2, and applying pressure to the sheet to transfer the roughened pattern of the sheet and roughen the surface of the support.
After the support has been roughened mechanically, it is preferably dipped in an acid or an aqueous alkali solution in order to remove abrasives and aluminum dust, etc. which have been embedded in the surface of the support. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid and hydrochloric acid, and examples of the alkali include sodium hydroxide and potassium hydroxide. Among those mentioned above, an aqueous alkali solution of for example, sodium hydroxide is preferably used. The dissolution amount of aluminum in the support surface is preferably 0.5 to 5 g/m2. After the support has been dipped in the aqueous alkali solution, it is preferable for the support to be dipped in an acid such as phosphoric acid, nitric acid, sulfuric acid and chromic acid, or in a mixed acid thereof, for neutralization.
Though there is no restriction for the electrolytic surface roughening method, a method in which the support is electrolytically surface roughened in an acidic electrolytic solution. Though an acidic electrolytic solution generally used for the electrolytic surface roughening can be used, it is preferable to use an electrolytic solution of hydrochloric acid or that of nitric acid. The electrolytic surface roughening method disclosed in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent O.P.I. Publication No. 53-67507 can be used. In the electrolytic surface roughening method, voltage applied is generally from 1 to 50 V, and preferably from 10 to 30 V. The current density used can be selected from the range from 10 to 200 A/dm2, and is preferably from 50 to 150 A/dm2. The quantity of electricity can be selected from the range of from 100 to 5000 C/dm2, and is preferably 100 to 2000 C/dm2. The temperature during the electrolytically surface roughening may be in the range of from 10 to 50° C., and is preferably from 15 to 45° C.
When the support is electrolytically surface roughened by using an electrolytic solution of nitric acid, voltage applied is generally from 1 to 50 V, and preferably from 5 to 30 V. The current density used can be selected from the range from 10 to 200 A/dm2, and is preferably from 20 to 100 A/dm2. The quantity of electricity can be selected from the range of from 100 to 5000 C/dm2, and is preferably 100 to 2000 C/dm2. The temperature during the electrolytically surface roughening may be in the range of from 10 to 50° C., and is preferably from 15 to 45° C. The nitric acid concentration in the electrolytic solution is preferably from 0.1% by weight to 5% by weight. It is possible to optionally add, to the electrolytic solution, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid or oxalic acid.
When the support is electrolytically surface roughened by using an electrolytic solution of hydrochloric acid, voltage applied is generally from 1 to 50 V, and preferably from 2 to 30 V. The current density used can be selected from the range from 10 to 200 A/dm2, and is preferably from 50 to 150 A/dm2. The quantity of electricity can be selected from the range of from 100 to 5000 C/dm2, and is preferably 100 to 2000 C/dm2. The temperature during the electrolytically surface roughening may be in the range of from 10 to 50° C., and is preferably from 15 to 45° C. The hydrochloric acid concentration in the electrolytic solution is preferably from 0.1% by weight to 5% by weight.
After the support has been electrolytically surface roughened, it is preferably dipped in an acid or an aqueous alkali solution in order to remove aluminum dust, etc. produced in the surface of the support. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid and hydrochloric acid, and examples of the alkali include sodium hydroxide and potassium hydroxide. Among those mentioned above, the aqueous alkali solution is preferably used. The dissolution amount of aluminum in the support surface is preferably 0.5 to 5 g/m2. After the support has been dipped in the aqueous alkali solution, it is preferable for the support to be dipped in an acid such as phosphoric acid, nitric acid, sulfuric acid and chromic acid, or in a mixed acid thereof, for neutralization.
The mechanical surface roughening and electrolytic surface roughening may be carried out singly, and the mechanical surface roughening followed by the electrolytic surface roughening may be carried out.
After the surface roughening, anodizing treatment may be carried out. There is no restriction in particular for the method of anodizing treatment used in the invention, and known methods can be used. The anodizing treatment forms an anodization film on the surface of the support. For the anodizing treatment there is preferably used a method of applying a current density of from 1 to 10 A/dm2 to an aqueous solution containing sulfuric acid and/or phosphoric acid in a concentration of from 10 to 50%, as an electrolytic solution. However, it is also possible to use a method of applying a high current density to sulfuric acid as described in U.S. Pat. No. 1,412,768, a method to electrolytically etching the support in phosphoric acid as described in U.S. Pat. No. 3,511,661, or a method of employing a solution containing two or more kinds of chromic acid, oxalic acid, malonic acid, etc. The coated amount of the formed anodization film is suitably 1 to 50 mg/dm2, and preferably 10 to 40 mg/dm2. The coated amount of the formed anodization film can be obtained from the weight difference between the aluminum plates before and after dissolution of the anodization film. The anodization film of the aluminum plate is dissolved employing for example, an aqueous phosphoric acid chromic acid solution which is prepared by dissolving 35 ml of 85% by weight phosphoric acid and 20 g of chromium (IV). oxide in 1 liter of water.
The support which has been subjected to anodizing treatment is optionally subjected to sealing treatment. For the sealing treatment, it is possible to use known methods using hot water, boiling water, steam, a sodium silicate solution, an aqueous dicromate solution, a nitrite solution and an ammonium acetate solution.
After the above treatment, the support is suitably undercoated with a water soluble resin such as polyvinyl phosphonic acid, a polymer or copolymer having a sulfonic acid in the side chain, or polyacrylic acid; a water soluble metal salt such as zinc borate; a yellow dye; an amine salt; and so on, for hydrophilization treatment. The sol-gel treatment support disclosed in Japanese Patent O.P.I. Publication No. 5-304358, which has a functional group capable of causing addition reaction by radicals as a covalent bond, is suitably used.
The prepared coating liquid for the image formation layer is coated on the support according to a conventional method, and dried to obtain a light sensitive planographic printing plate precursor. Examples of the coating method include an air doctor coating method, a blade coating method, a wire bar coating method, a knife coating method, a dip coating method, a reverse roll coating method, a gravure coating method, a cast coating method, a curtain coating method, and an extrusion coating method.
In the invention, the imagewise exposed image formation layer, which are cured are at exposed portions, is developed with an alkali developer, whereby the image formation layer at exposed portions are removed to form an image.
As the alkali developer, a conventional alkali aqueous solution is used. For example, there is an alkali developer containing an inorganic alkali agent such as sodium silicate, potassium silicate, ammonium silicate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate; sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate; sodium carbonate, potassium carbonate, ammonium carbonate; sodium borate, potassium borate, lithium borate; sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
The alkali developer can contain organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, and pyridine.
These alkali agents can be used singly or as a mixture of two or more thereof. The alkali developer can contain an anionic surfactant, an amphoteric surfactant, or an organic solvent such as alcohol.
In the invention, a DMD is a reflection element in which a lot of micro-mirrors are arranged. The DMD ordinarily comprises about 1.3 million micro-mirrors per 2 cm2 of DMD. The arrangement and the number of the micro-mirrors correspond to those of pixels in image data. The direction of each micro-mirror can be varied corresponding to each of image information in image data. When parallel rays are irradiated onto the reflection element, the reflection element reflects the rays according to image information so as to focus onto an imaging material, whereby an image is formed on the imaging material. Generally, an exposure device employing DMD comprises, in addition to the reflection element, a light source element (having a light source, a condenser, a lens and a mirror) producing parallel rays and an image formation element (having a lens and a mirror) for focusing the reflected rays onto an imaging material.
In the invention, a light source is used which is capable of emitting an ultraviolet light, and preferably a 350–450 nm ultraviolet light. Examples of the light source include high pressure mercury lamp, ultra-high pressure mercury lamp, a halogen lamp, and a metal halide lamp.
An ultraviolet light corresponding to digital image formation can be irradiated onto an imaging material employing a DMD. There is disclosure of an exposure device and exposure method for a printing plate material employing a DMD in WO 97/21151, 97/39277, 98/47048, 00/212735, and 00/36470, and U.S. Pat. No. 5,579,240.
The exposure device in
The light source element 1 is comprised of a lamp 11, a condenser 12, a lens 13, and a mirror 14. The lamp 11 emits ultraviolet rays. The lamp 11 of
In the reflection element 2, corresponding to a DMD, a lot of micro-mirrors 2a, 2b, 2c, 2d, 2e, 2f, and 2g are arranged. The number and arrangement of the micro-mirrors correspond to those of pixels in image data. The distance between any two micro-mirrors adjacent to each other is preferably from 1 to 100 μm. The direction of each micro-mirror can be varied corresponding to each of image information in image data. A DMD available on the market is constructed so that direction of the micro-mirrors varies by an angle of ordinarily 10 degrees.
In
As is described above, before exposure is carried out, direction of each mirror varies corresponding to each of pixel information in the image data.
Image formation element 3 in
It is preferred that pixel images are formed on the surface of the planographic printing plate material 4 at an interval of from 0.5 to 50 μm. The planographic printing plate material 4 comprises a hydrophilic support 42 and an image formation layer 41. In a photocurable image formation layer, the image formation layer at exposed portions 41a is cured. In a photo-solubilization image formation layer, the image formation layer at exposed portions 41a is soluble. In a photopolymer type image formation layer, the image formation layer at exposed portions 41a is photo-polymerized. In any image formation layer described above, no substantial change occurs at the image formation layer at unexposed portions 41b.
Next, the present invention will be explained in the following examples, but the present invention is not limited thereto. In the examples, “parts” represents “parts by weight”, unless otherwise specified.
<<Preparation of Light Sensitive Planographic Printing Plate Material Samples>>
(Synthesis of Binder 1)
Thirty parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol, and 3 parts of α,α′-azobisisobutyronitrile were put in a three neck flask under nitrogen atmosphere, and reacted under nitrogen atmosphere for 6 hours at 80° C. in an oil bath. After that, the reaction mixture was refluxed at a boiling point of isopropyl alcohol for one hour, and 3 parts of triethylbenzylammonium chloride and 25 parts of glycidyl methacrylate were further added to the mixture, and reacted for additional 3 hours. The resulting reaction mixture was added with propylene glycol monomethyl ether to give a solution having a solid content of 20% by weight. Thus, a binder 1 solution was obtained.
The weight average molecular weight of the binder 1 was 35,000, measured according to GPC. The glass transition temperature Tg of the binder 1 was 85° C., measured according to DSC (differential thermal analysis). The acid value of the binder 1 was 70.
<<Preparation of Support 1>>
A 0.3 mm thick aluminum plate (material 1050, refining H16) was degreased at 60° C. for one minute in a 5% sodium hydroxide solution, washed with water, immersed at 25° C. for one minute in 10% hydrochloric acid solution to neutralize, and then washed with water. The resulting aluminum plate was electrolytically etched using an alternating current at 25° C. for 60 seconds at a current density of 100 A/dm2 in a 1.0 weight % hydrochloric acid solution, desmut at 60° C. for 10 seconds in a 5% sodium hydroxide solution. The desmut aluminum plate was anodized at 25° C. for 1 minute at a current density of 10 A/dm2 and at a voltage of 15 V in a 15% sulfuric acid solution, and further subjected to hydrophilization treatment at 75° C. in an aqueous 1% polyvinyl phosphonic acid solution. Thus, support 1 was obtained. The center line average surface roughness (Ra) of the support was 0.65 μm.
(Preparation of Light Sensitive Planographic Printing Plate Material Sample 1)
The following image formation layer coating solution 1 was coated on the support 1 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the following oxygen-shielding layer coating solution 1 was coated on the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 1 was prepared.
(Image formation layer coating solution 1)
η-Cumene-(η-cyclopentadienyl)iron-
3.0 parts
hexafluorophosphate
Sensitizing dye, Dye 03
4.0 parts
Binder 1 solution
45.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
30.0 parts
Tetraethylene glycol dimethacrylate
5.0 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
2-t-Butyl-6-(3-t-butyl-2-hydroxy-5-
0.5 parts
methylbenzyl)-4-methylphenylacrylate
(Sumirizer GS: produced by Sumitomo 3M Co., Ltd.)
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
(Oxygen-shielding layer coating solution 1)
Polyvinyl alcohol, Gosenol AL-05
85.0 parts
(produced by Nippon Gosei Kagaku Kogyo Co., Ltd.)
Polyvinyl Pyrrolidone, Rubitec K-30
15.0 parts
(produced by BASF Co., Ltd.)
Surfinol 465
0.2 parts
(produced by Air Products Co., Ltd.)
Water
900 parts
(Preparation of Light Sensitive Planographic Printing Plate Material Sample 2)
The following image formation layer coating solution 2 was coated on the support 1 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the oxygen-shielding layer coating solution 1 above was coated on the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 2 was prepared.
(Image formation layer coating solution 1)
η-Cumene-(η-cyclopentadienyl)iron-
2.0 parts
hexafluorophosphate
2,2′-Bis(2-chlorophenyl)-4,5,4′,5′-
12.0 parts
tetraphenylbisimidazole
Sensitizing dye, Dye 15
4.0 parts
Binder 1 solution
45.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
30.0 parts
Tetraethylene glycol dimethacrylate
5.0 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
2-Mercaptobenzothiazole
1.5 parts
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
0.2 parts
Sanol LS770, produced by Sankyo Raifutekku Co., Ltd.)
2,4,6-Tris(dimethylaminomethyl)phenol
1.5 parts
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
(Preparation of Light Sensitive Planographic Printing Plate Material Sample 3)
The following image formation layer coating solution 3 was coated on the support 1 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the oxygen-shielding layer coating solution 1 above was coated on the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 3 was prepared.
(Image formation layer coating solution 3)
Tribromoacetyl compound, BR 22
7.0 parts
Sensitizing dye, Dye 01
4.0 parts
Binder 1 solution
45.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
30.0 parts
Tetraethylene glycol dimethacrylate
5.0 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
0.2 parts
Sanol LS770, produced by Sankyo Raifutekku Co., Ltd.)
2,4,6-Tris(dimethylaminomethyl)phenol
1.5 parts
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
(Preparation of Light Sensitive Planographic Printing Plate Material Sample 4)
The following image formation layer coating solution 4 was coated on the support 1 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the oxygen-shielding layer coating solution 1 above was coated oh the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 4 was prepared.
(Image formation layer coating solution 4)
η-Cumene-(η-cyclopentadienyl)iron-
3.0 parts
hexafluorophosphate
Tribromoacetyl compound, BR 22
1.5 parts
Sensitizing dye, Dye 06
4.0 parts
Binder 1 solution
45.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
30.0 parts
Tetraethylene glycol dimethacrylate
5.0 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
0.2 parts
Sanol LS770, produced by Sankyo Raifutekku Co., Ltd.)
2,4,6-Tris(dimethylaminomethyl)phenol
1.5 parts
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
(Preparation of Light Sensitive Planographic Printing Plate Material Sample 5)
The following image formation layer coating solution 5 was coated on the support 1 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the oxygen-shielding layer coating solution 1 above was coated on the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 5 was prepared.
(Image formation layer coating solution 5)
Tribromoacetyl compound, BR 22
1.5 parts
2,2′-Bis(2-chlorophenyl)-4,5,4′,5′-
12.0 parts
tetraphenylbisimidazole
Sensitizing dye, Dye 06
4.0 parts
Binder 1 solution
30.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
40.0 parts
Tetraethylene glycol dimethacrylate
10.0 parts
2-Mercaptobenzothiazole
1.5 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
0.2 parts
Sanol LS770, produced by Sankyo Raifutekku Co., Ltd.)
2,4,6-Tris(dimethylaminomethyl)phenol
1.5 parts
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
[Preparation of Light Sensitive Planographic Printing Plate Material Sample 6]
(Preparation of Support 2)
Support 2 was prepared in the same manner as in support 1 of Example 1, except that hydrophilization treatment was carried out, employing an aqueous 1.5% sodium silicate A solution instead of an aqueous 1% polyvinyl phosphonic acid solution.
The following image formation layer coating solution 6 was coated on the support 2 through a wire bar, and dried at 95° C. for 1.5 minutes to give an image formation layer having a dry thickness of 2.0 g/m2. Subsequently, the oxygen-shielding layer coating solution 1 above was coated on the resulting image formation layer through a wire bar, and dried at 75° C. for 1.5 minutes to give an oxygen-shielding layer having a dry thickness of 1.5 g/m2. Thus, light sensitive planographic printing plate material sample 6 was prepared.
(Image formation layer coating solution 6)
Diazo resin-1
7.0 parts
(Condensation product of
4-diazonium-3-methoxydiphenylamine
hexafluorophosphate with formaldehyde)
Tribromoacetyl compound, BR 22
1.5 parts
Sensitizing dye, Dye 06
2.0 parts
Binder 1 solution
45.0 parts
(in terms of
solid content)
Polyfunctional oligomer M-8
30.0 parts
Tetraethylene glycol dimethacrylate
5.0 parts
2-Mercaptobenzothiazole
1.5 parts
30% phthalocyanine pigment dispersion
10.0 parts
(MHI 454 produced by Mikuni Sikisosha)
Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
0.2 parts
Sanol LS770, produced by Sankyo Raifutekku Co., Ltd.)
2,4,6-Tris(dimethylaminomethyl)phenol
1.5 parts
Fluorine-contained surfactant
0.5 parts
(F-178K: produced by Dainippon Ink Co., Ltd.)
Methyl ethyl ketone
80 parts
Cyclohexanone
820 parts
[Preparation of Light Sensitive Planographic Printing Plate Material Sample 7]
Light sensitive planographic printing plate material sample 7 was prepared in the same manner as in planographic printing plate material sample 6, except that the oxygen-shielding layer coating solution 1 was not coated.
[Preparation of Light Sensitive Planographic Printing Plate Material Sample 8 (Comparative)]
Light sensitive planographic printing plate material sample 8 (comparative) was prepared in the same manner as in planographic printing plate material sample 7, except that the tribromoacetyl compound BR 22 was eliminated from the image formation layer coating solution 6.
<<Evaluation of Light Sensitive Planographic Printing Plate Material Samples>>
The light sensitive planographic printing plate material samples obtained above were evaluated according to the following method.
(Measurement of Sensitivity)
Each of the planographic printing plate material samples obtained above was imagewise exposed, employing a DVD exposure device (UV setter 710S/HS, produced by basisPrint Co., Ltd., and available from Toyo Ink Manufacturing Co., Ltd.) equipped with a 350–450 nm ultraviolet light source. The image pattern used for the exposure comprised a solid image and a square dot image with a screen number of 175 LPI and a 50% dot area. Subsequently, the exposed sample was subjected to development treatment employing a CTP automatic developing machine (Raptor Thermal produced by Glunz & Jensen Co., Ltd.) to obtain a planographic printing plate. Herein, the developing machine comprised a development section charged with developer having the following developer composition, a washing section for removing the developer remaining on the developed sample after development, and a gumming section charged with a gumming solution (a solution obtained by diluting GW-3, produced by Mitsubishi Chemical Co., Ltd., with water by a factor-of 2).for protecting the surface of the developed sample.
The lowest exposure energy amount (μJ/cm2) reproducing the solid image without reduction of the layer thickness in the resulting planographic printing plate was defined as exposure energy and evaluated as a measure of sensitivity. The less the exposure-energy is, the higher the sensitivity.
<Composition of developer (aqueous solution containing the
following components)>
Potassium silicate A aqueous solution
8.0% by weight
(containing 25.5–27.5% by weight of SiO2 and
12.5–14.5% by weight of K2O)
Newcol B-13SN (produced by
3.0% by weight
Nippon Nyukazai Co., Ltd.)
Potassium hydroxide
amount giving pH 12.3
(Printing Durability)
The printing plate material sample obtained above was exposed at an exposure amount of 200 μJ/cm2, employing an image with a screen line number of 175, and developed with the developer, whereby a printing plate was obtained. Employing the resulting printing plate, printing was carried out on a press (DAIYA1F-1 produced by Mitsubishi Jukogyo Co., Ltd.), wherein a coat paper, printing ink (Soybean oil ink, “Naturalith 100” produced by Dainippon Ink Kagaku Co., Ltd.), and dampening water (SG-51, H solution produced by Tokyo Ink Co., Ltd., Concentration: 1.5%) were used. The number of prints printed time when printing started until time when dot reduction at highlight portions was defined as a measure of printing durability.
(Chemical Resistance)
The printing plate material sample obtained above was exposed at an exposure amount of 200 μJ/cm2, employing an image with a screen line number of 175, and developed with the developer, whereby a printing plate was obtained. Employing the resulting printing plate, printing was carried out employing a press GTO (produced by Heiderberg Co., Ltd.), wherein a coat paper sheet, printing ink (Soybean oil ink, “Naturalith 100” produced by Dainippon Ink Kagaku Co., Ltd.), and dampening water (an H liquid, SG-51 produced by Tokyo Ink Co., Ltd., Concentration: 1.5%) were used. A cycle was repeated in which printing was stopped, when 500 sheets were printed, and the printing plate surface was wiped with a sponge impregnated with an ultra plate cleaner (available from Dainichi Seika Co., Ltd.), and allowed to stand for 3 minutes, and printing was restarted. The minimum number of cycles in which reduction of dots at highlight portions was observed was evaluated as a measure of chemical resistance. The results are shown in Table 1.
TABLE 1
Light sensitive
planographic
printing plate
Printing
Chemical
material sample
Sensitivity
durability
resistance
No.
(μJ/cm2)
(number)
(number)
Remarks
1
70
400,000
55
Inv.
2
80
350,000
50
Inv.
3
140
300,000
50
Inv.
4
70
350,000
50
Inv.
5
80
400,000
45
Inv.
6
40
400,000
50
Inv.
7
180
350,000
50
Inv.
8
200
70,000
5
Comp.
Inv.: Inventive,
Comp.: Comparative
As is apparent from Table 1, the inventive light sensitive planographic printing plate material samples provide high sensitivity, printing durability and chemical resistance, as compared with the comparative light sensitive planographic printing plate material sample.
Kuroki, Takaaki, Matsumura, Toshiyuki
| Patent | Priority | Assignee | Title |
| Patent | Priority | Assignee | Title |
| 4987056, | Jun 02 1988 | Toyo Boseki Kabushiki Kaisha | Photopolymerizable composition |
| 6140025, | Sep 16 1998 | Kansai Paint Co., Ltd. | Negative type photosensitive resin composition and method for forming resist pattern |
| 20030010240, | |||
| 20040005515, | |||
| 20040091816, | |||
| 20040157154, | |||
| 20040191691, | |||
| 20050048403, | |||
| 20050196700, | |||
| EP1413925, | |||
| EP1445653, | |||
| EP1452916, | |||
| EP1513015, | |||
| JP2003223007, |
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